JPS62187772A - Lacquer or forming composition and method of rendering non-tackiness properties and improving lubricancy to composition - Google Patents

Abstract

Lacquers and molding compositions containing an anti-adhesive character producing and lubricity increasing amount of a polyester-containing polysiloxane corresponding to the formula <IMAGE> (I) wherein A, B and D each represent -CH3 or -Z-R-Q; Z represents an alkylene group with 1 to 11 carbon atoms, -(CH2)2SCH2-or -(CH2)3NHCO-; R represents an aliphatic, cycloaliphatic or aromatic group containing at least 3 carboxylate ester groups and having an average molecular weight &upbar& M of 300 to 3,000; Q represents a reactive group capable of chemically reacting with a resin component of the lacquer or molding composition; x represents a number from 4 to 150; y represents a number from 1 to 6, in which an average molecule contains at least one group -Z-R-Q and the ratio of the number of -Z-R-Q groups to the number x is from 1:3 to 1:30. A process for imparting anti-adhesive character and increasing lubricity of lacquers and molding compositions by incorporating such polyester-containing polysiloxanes into the compositions as additives is also disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to coating compositions or lacquers and molding compositions with foot polysiloxanes that produce non-stick properties and increase lubricity. More particularly, the present invention relates to the use of certain identified polysiloxanes to produce non-stick properties in lacquers and molding compositions as described below.

[Prior art and its problems] Contamination resistance (so!1-rcsis) is improved by the resulting boundary layer.
It is known to add polysiloxanes to coating compositions or lacquers in order to obtain t) surfaces. In addition, the scratch resistance of its surface
b resistance and lubricity are improved by the addition of the polysiloxane.

Polysiloxanes are also added to molding compositions to facilitate release from the mold of articles molded according to molding methods involving chemical crosslinking reactions under the influence of elevated temperatures.

The properties of the molded non-adhesive surface layer described above are particularly important for surfaces that are expected to be soiled or damaged, the facades of buildings, for example by graffiti being applied with spray paint. In the event of such vandalism, the front surface protected with a non-stick product can be easily cleaned again.

The use of polysiloxanes in paints or lacquers prevents scratches and markings.
Furniture surfaces are also imparted with greater scratch resistance so that the visible abrasion results that occur during daily use such as scratches can be significantly reduced.

In addition, polysiloxane modified binder (polysiloxane modified binder)
nders) are used in coating papers that exhibit the non-stick action of known so-called release papers.

Dimethylpolysiloxane, methylphenylsiloxane, polyalkylene-modified dimethylpolysiloxane, reactive polydimethylpolysiloxane,
and hydroxy-functional polyether siloxanes. The use of these products is described in West German Patent Nos. 1,111,320 and 1,092,585, European Patent Publication No. 1
11i, 9 [1G and 103,367, U.S. Patent No. 4.07 [i, 695 and pamphlet]
J (Goldsmith Internal) (Gold
(Published July 1982, Volume 5B, Page 2) and Fatlpee Congress Book (Fattlpee Congress [3o
OK) (published in I903, p. 332) as well as the 6th International Technical Conference: Inbrobd. 171 in the SPI newsletter.
M-Processing with Silicone Internal Mold Release Technology (Improve)
d RIM-Processingvlth 5ili
cone Internal Mold Relea
seTechnology) This technology has been described.

Surface activity is a property of each of these aforementioned polysiloxanes, which occur in abundance so as to produce the desired properties at liquid/gas or solid/gas interface surfaces: reduced tackiness, increased lubricity. It is said to belong to

In silicone-modified binders, the polysiloxane groups are fixedly incorporated into the binder by polyaddition and polycondensation, so that the silicone-modified binders are an independent class of coating compositions that cannot be compared with the aforementioned polysiloxanes. Configure. Although these silicone resins essentially satisfy the requirements placed on them for non-stick properties, due to their high silicone content, they are very expensive and therefore have a certain limited Can only be used within a range.

Apart from reactive polysiloxanes, the structure of these polysiloxanes is an inert material with respect to reactivity with lacquers and molding compositions. The effects achieved by using polysiloxanes to reduce liveliness or increase lubricity result in short-lasting effectiveness. This is because the surface orientation (surrac
This is because these polysiloxanes are easily wiped off or washed away with solvents due to their orientation (orientation), thereby losing their effectiveness.

Because polysiloxanes carrying reactive functional groups are insoluble, they tend to separate and do not pass through the reaction system while the resin of the lacquer binder or the resin of the molding composition reacts itself. Polysiloxanes are very difficult to incorporate into lacquers or molding compositions, since they are not evenly distributed and are only partially incorporated into the product. Attempts have been made to avoid such drawbacks by incorporating such reactive polysiloxanes into reactive resins during their manufacture. However, the mobility of the polysiloxane is thereby adversely affected and orientation to the surface is substantially hindered, so that relatively large amounts of polysiloxane must be utilized to obtain the desired non-stick effect. Must be.

The use of carboxy-functional siloxanes in polyurethane systems according to U.S. Pat. Polymers of the kind described in U.S. Pat. No. 4,070. Since siloxane exhibits incompatibility, the cell structure
The collapse of e) occurs during foaming, especially during foaming of polyurethane, resulting in an irregular structure.

Polyether-based polysiloxanes are difficult to react to when affected by oxygen due to the structure of the polyether, since the breaking of the polyether chains occurs at temperatures above 150°C without disturbing the lacquer resin or molding composition. Limited to temperature stability only.

[Problem to be Solved by the Invention] It is an object of the present invention to provide coating compositions, such as paints or lacquers and molding compositions, which confer non-stick properties and which can largely or completely avoid the above-mentioned negative properties. The object of the present invention is to provide a polysiloxane that increases lubricity.

A particular object of the present invention is to provide polysiloxanes that can provide increased non-stick and lubricity properties with long lasting effects.

The present invention also eliminates the need for large amounts of polysiloxane components incorporated into the lacquer or molding composition.
It is also an object to provide polysiloxanes which provide non-stick properties to lacquers or molding compositions and which provide improved lubricity.

A further aspect of the invention is to provide polysiloxanes which can be incorporated individually or separately into lacquers or molding compositions.

Another object of the present invention is to provide polysiloxanes which can provide non-destructive properties and improve the lubricity of lacquers or molding compositions in an economical manner.

It is also an object of the present invention to provide polysiloxanes capable of providing non-stick properties and improving the lubricity of lacquers or molding compositions in an ecologically sound manner.

Yet another object of the invention is to provide a method for imparting non-stick properties and improving the lubricity of lacquers or molding compositions.

Means for Solving the Problems The present invention provides an average formula (I) of melon which produces effective anti-stick properties and increases lubricity: (wherein the A, B and D groups are each -CHI group or -Z-R-Q!!, two groups have 1 to 11 carbon atoms
alkylene group, -(CH2)23CH2- group or -
(CH2)3 represents a NIICU- group; the R group contains at least 3 carboxylate ester bonds;
an aliphatic group having an average molecular weight n of 300 to 3000;
Represents a cycloaliphatic group or aromatic group; Q group represents a reactive group capable of chemically reacting with the resin component of the resulting composition;
X is 4 to 150, y is not 1 to 6; the average molecule has at least one -Z-R-Q group hexagonal, and -Z-R-
A lacquer or molding composition consisting of a polyester-containing polysiloxane in which the ratio of the number of Q groups to the number imparting non-stick properties to a composition selected from the group consisting of lacquers and molding compositions and providing lubrication thereof, comprising the step of incorporating an average amount of a polyester-containing polysiloxane of formula (I) into the resulting composition. Concerning how to improve sex.

EXAMPLES The present invention provides a coating composition, i.e. an amount of a polysiloxane which produces non-stick properties and/or increases lubricity, wherein the polysiloxane has an average formula (I); Each group independently represents -C)13 or -Z-
R-Q group, the average molecule has at least one -Z-
contains R-Q groups; 2 groups represent alkylene groups with 1 to 11 carbon atoms, -(CH2)25C)h- groups or -(CH2)3NIIGO- groups; at least 3 R groups contains carboxylate ester bonds of Show; X is 4~
an integer of 150, y represents an integer of 1 to 6; the average molecule contains at least one (7)-Z-R-Q group, and -Z-R
- The ratio of the number of Q groups to the number X is 1:3 to 1:30. relating to things.

As used herein, "lacquer" refers to a coating composition that is applied to a substrate in liquid form and creates a protective or sensory and/or decorative surface through the formation of a film. do. Substrates to which polysiloxane-containing lacquers are applied in the present invention include, for example, wood, metal, synthetic plastic films or webs, synthetic plastic parts, paper, leather and structural materials such as brick, concrete and plaster. It will be done. The present invention relates to unpigmented, pigmented and/or dye-bearing lacquers which can contain binders of varying nature. Coatings within the scope of the invention include, for example, P
Data storage media (dat), such as C203 and C'02
These include those containing magnetic pigments used in the manufacture of electronic carriers. Also included within the scope of this invention are compositions that form permanent lubricious coatings.

The reactive groups of the polysiloxanes of the invention should be matched with the crosslinking or curing mechanism (IIccbanism) of the lacquer composition or molding composition involved, i.e. the binder containing the lacquer or the respective molding composition. be. Examples of mechanisms that proceed in different ways include, for example, acrylate-1-/isocyanate lacquer (RUR-lac
quers) and polyaddition mechanisms such as epoxy resins, such as acrylate/amino blast resin lacquers, alkyd/amino blast resin lacquers, saturated polyester resin lacquers and modified amino blast resin lacquers such as melanin resin lacquers and urea resin lacquers. polymerization mechanisms in lacquer compositions and unsaturated polyester resin lacquers which are cured by radical polymerization initiated by high energy radiation such as ultraviolet radiation or electron beam radiation or by peroxides.

These lacquers, as known to those skilled in the art, include:
The liquid phase includes a solvent and/or water. The liquid phase is also present in the form of monomeric or low molecular weight compounds that react with other binder components to form the lacquer coating.

The lacquers of the invention are also so-called powder lacquers, which do not have any liquid phase and are applied in the form of a powder to the substrate to be coated, causing a reaction on the substrate.
r 1acquer).

Powder lacquers are often applied using the so-called electrostatic coating method (e
lecirostatic eoattng proc
(Oss) (Feltman (Ikoe I
``Korrosio Zuft Dorch Kunststofburger'' (author)
nsscbutz durcbKunstsorl'p
ulver)J (Corrosion Protect)
tion by Synthetic Ba5inPo
wer), Hemieanlagen Land Ververren; Chemical Plant Ant-Process (Ch.
amjcanlagcn undVcrl'al+re
n; Cbcm1cal Plants a
nd Processes), October 1984,
(See pages 87-94).

The lacquers of the invention thus have essentially the same basic composition as known lacquers containing siloxanes as additives. Otherwise, the lacquers of the invention can be used, for example, by crosslinking agents, dispersants, fillers, catalysts and/or hardening accelerators, the rheological (rl+aological) of the lacquer;
tl) Common lacquer additives, such as substances that influence properties, are also subject to 6H.

In a similar concept, the same applies to molding compositions as described above for lacquers. "Molding composition" means Inasses that are processed to produce shaped objects, the reactive resins contained in the Inasses being processed during the molding process, generally at elevated temperatures. A reaction occurs between. Molding compositions in the sense of the invention include, for example, those based on unsaturated polyester resins and vinyl resins, and also those based on polyester resins with reduced shrinkage (s).
Also included are combinations with thermoplastics such as polystyrene, polyvinyl acetate, polymethyl methacrylate and styrene-butadiene copolymers, which may be added as a linkage-rOducing component. Furthermore, molding compositions are used, inter alia, for example in the reaction injection molding process.
ng process (formerly known as M), and includes polyurethane and polyamide, which are particularly difficult to release from the mold.

Other molding compositions are made based on epoxy resins. Epoxy resins are used in casting compositions.
Bosltions) and extrusion compositions (press
It is preferably used in the field of compositions. Furthermore, for example, a wet compaction step (wet p
(ressing process), injection process (inj
ect 1 on process) or profile drawing process (prolilc drawing p
Molding compositions that can be processed using phenolic resins include phenol-based resins, generally referred to as phenolic resins.
Contains formaldehyde synthetic resin.

The molding compositions may also generally contain conventional additives or other ingredients according to the statements of those skilled in the art already mentioned with respect to lacquers. In particular, the molding composition contains fillers and/or reinforcements such as, for example, glass fibres, carbon fibres, polyamide fibres, wollastonite, silicates, inorganic carbonates, aluminum hydroxide, barium sulphate or kaolin. A filler may also be included.

The polysiloxane used in the present invention can be used in coil coating plants.
), for example at temperatures up to 250°C, such as those encountered in
Since they are very thermally stable at temperatures up to about 350° C. and relatively short reaction times, they have a particularly beneficial effect in thermosetting lacquers. In such an environment, hydroxy-terminated polyether siloxanes degrade as the polyoxyalkylene groups thermally decompose under these conditions.
It cannot be used.

According to the invention, it has been found that R groups denoting compounds or groups containing at least three carboxylate ester groups exhibit very good compatibility in modern lacquers and molding composition resins. .

The amount of polysiloxane added to lacquers and molding compositions is very high according to the state of the art;
The desired effects in terms of sufficient anti-stick properties and increased lubricity have been achieved. A very small amount, for example 0.05% by weight, based on the total weight of the lacquer or molding composition, can produce a remarkable effect. Preferably,
The amount of polysiloxane is at least about 0.1% by weight, particularly preferably at least 0.5% by weight, based on the total weight of the lacquer or molding composition. Since polysiloxane is relatively expensive and expensive, the upper limit of polysiloxane content should be set to achieve sufficient effect and keep the amount as low as possible! 7, and over-addition is generally avoided for cost-L reasons. The upper limit is generally about 5% by weight, preferably about 3% by weight, based on the total weight of the lacquer or molding composition.
The amount is particularly preferably about 2% by weight.

The R groups form an important part of the composition of the polysiloxanes used in the invention. This is a carboxylate ester containing group. These groups are preferably bonded to each other by difunctional hydrocarbon groups having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms.

Saturated aliphatic hydrocarbon groups having 5 carbon atoms are preferred. The R group is preferably a polycaprolactone group formed by polymerization of caprolactone, as detailed hereinafter.

A group and B group represent -Z -R -Q group, and D group represents -
Preferably it represents a C83 group. These are so-called linear siloxanes. -Z -R-Q The ratio of the number of groups and the number X is 1
It is more preferably in the range of :3 to 1:25, preferably in the range of 1:5 to 1:15.

Another preferred example is that the A and B groups represent a -CH3 group and the D group represents a -Z-R-Q group. In this case, the ratio of the number of -Z-R-Q groups to the number X is 1=3
to 1:25, preferably I:4 to 1:1 (particularly preferably in the range I).

The polysiloxane used in the present invention containing carboxylate ester groups is, for example, represented by the following formula (I1
~-2 (in the formula: X represents 4 to 150, y represents 1 to 6, Z
'Ha 1011 SI atoms, -COOII group or -N
82) can be made with reactive functional siloxanes, as described, according to the reaction mechanism applicable to the difunctional group attached to the 82 group.

These functional polysiloxanes are partially commercially available or are available from, for example, West Deutsche Pat. 4.076.09
Specification No. 5, Specification No. 3.481,9G9, No. 3
, 442,925, 3,507,499, and 2,947,771.

Determination of the equivalent weight of siloxane starting material required for further reaction to form the ester group-containing polysiloxane in this invention is done by determining the hydroxyl group, acid value or amine value.

beta-propiolactone, delta-valerolactone,
Lactones such as epsilon-caprolactone and dodecalactone or their substituted derivatives and formulas (Ill,
The reaction of the 011 functional polysiloxane corresponding to (Ill) or N takes place by a ring-opening esterification method. Examples of polymerizable lactones and methods for their polymerization are found in US Pat. No. 4,3130,643, incorporated herein by reference.

The 011 group required to initiate ring-opening polymerization is 011
The chain length of the polyester obtained by group-functional polysiloxanes is determined by the molar amount of lactone used by the hydroxyl groups. Lactone polymerization can be carried out, for example, in a suitable solvent such as high-boiling gasoline fractions, alkylbenzenes, esters or ketones or by direct melting of about 100
The reaction of p-toluenesulfonic acid or dibutyltin dilaurate at a temperature of -180 DEG C. then proceeds, for example, according to the following formula (1): (1) H3 (2).

Polysiloxanes containing terminal hydroxylated polyester groups are obtained in this way in such a way that the Q groups in this case represent 011 groups. Polyesters formed from such lactones conveniently have an average molecular weight Mn of about 300 to 3000, preferably about 500 to 1,500.

However, if the Q group represents a COO11 functional group, the reaction described above may be carried out in any suitable manner to form the free carboxylic acid group, such as ring-opening the ester with a dicarboxylic or tricarboxylic anhydride. It will be further promoted according to the This reaction is carried out, for example, according to the following formula (X):

Suitable dicarboxylic or tricarboxylic anhydrides include, for example, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and 1,2,4-benzene. Contains tricarboxylic anhydride.

If the Q group is an -NCO group, the reaction example described by formula (I) or formula (XV) is such that the 011 group of the polyisocyanate group is preferably reacted. Hydroxy-functional polyester in proportion to polyisocyanate,
Preferably, the reaction proceeds further when reacting with a diisocyanate.

This can be achieved, for example, by utilizing polyisocyanates with isocyanate groups having different reactivities. Such isocyanates include, for example, isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate). In this diisocyanate,
An incyanate group attached to a cycloaliphatic group is less reactive than a COOH group attached to an aliphatic group by a factor of IO.

In addition, the reaction route is a single adduct (IIlon).

The use of a polyisocyanate with a larger molar amount compared to the available 011 groups required for the formation of a single adduct can lead to the formation of a single adduct.

Excess polyisocyanate is removed by vacuum distillation, preferably by thin-layer evaporation.
r).

The described reaction has, for example, the following reaction mechanism (X+): (xl) GO Occurs according to.

If the Q group is a -CIl-CIlr group, then the formula (I
The reaction examples described under X) or formula (XV) are further advanced by reacting the hydroxy-functional polyester with, for example, acrylic acid chloride or methacrylic acid chloride. This can be effectively carried out in a medium in which the hydrogen chloride to be removed is taken up in the form of a salt, for example in pyridine.

The reaction described is e.g. the following reaction mechanism (Xl+)
: Occurs according to.

Salt formation with carboxy-functional polysiloxanes
This takes place in a known manner, for example by reacting the siloxane with an alkali carbonate or an alkali bicarbonate, with the exception of CO2 and 820.

The resulting water can be removed under mild azeotropic conditions, for example in toluene or under vacuum. The reaction takes place, for example, according to the following reactor tM(Xlll):

Suitable cations for salt formation include lithium, sodium, potassium ions.

In the present invention, amine salts of carboxy-functional polysiloxanes are particularly suitable for forming non-stick layers in polyurethane molding compositions. Particularly suitable amines for the salt-forming reaction are those conventionally used in polyurethane systems such as those used as catalysts. Thus, for example, triethylenediamine (DABCO
(2), benzyldimethylamine, triethylamine, and/or N-alkylmorpholine are preferably used as cations. When such amines are used to neutralize carboxy-functional polysiloxanes, they have no or only a minor effect on the overall course of the crosslinking reaction in polyurethane systems.

The reaction of the -OH, -Coo)I or -NH2 functional polysiloxanes with dicarboxylic acids and/or anhydrides and diols takes place according to known condensation methods suitable for forming polyesters.

Depending on the relative molar ratio of dicarboxylic acid and/or dicarboxylic anhydride and diol used, the polysiloxane end groups formed during the condensation reaction can be -COO
It is controlled according to the formation of H or -OH end groups.

Such a reaction, for example, has the following reaction mechanism (X1v
): occurs according to. Also, if an amino-functional siloxane is used, the reaction follows the reaction mechanism (
XV): Occurs according to. Desirably, these polyesters have an average molecular weight Mu of about 300-2500, preferably about 500-1500.

By varying the structure of the polyester, for example by appropriate selection of diols, dicarboxylic anhydrides and/or dicarboxylic acids used in a number equal to the number of ester groups, the desired degree of compatibility can be achieved for lacquers or moldings. This is accomplished by a polymer used as a binder in the composition. This plays an important role especially when binders with different polarities are used. Phthalate polyester-modified siloxanes are also used in q-effects for binders based on phthalate esters, for example. Caprolactone polyester-modified siloxanes are particularly preferred because they exhibit high compatibility with most different polymer systems.

From the foregoing description, the aliphatic, cycloaliphatic and aromatic polyester groups conventionally used and known in the art to be advantageous for the production of polyesters for lacquers and molding compositions are used. It turns out that you can. Said diols are preferably selected from ready-to-use C2 to CI2 compounds, while dicarboxylic acids are preferably selected from those having 2 to 10 carbon atoms in the alkylene chain. A cyclohexane group is preferred as a cycloaliphatic group, and a phenyl group is preferred as an aromatic group.

The two groups serve to bond the silicon atom to the carboxylate ester group U. The nature of this bifunctional merging group, as known in the art of siloxane chemistry, depends on the starting materials used to make the siloxane in the present invention and the nature of the reaction (among others, U.S. Pat. 3.960.574 specification column 1). appropriate 2
Examples of functional linking groups are preferably alkylene groups with 2 to 4.10 or 11 carbon atoms, since the corresponding starting materials are particularly easy to obtain. The difunctional group may also be an alkylene group containing a thioether group (-3-). If the reaction is initiated with an amino group-containing siloxane, the linking group will be an alkylene amide group.

The Q group provides a conformal bond to the carboxylate ester group-containing white polysiloxane in the lacquer or molding composition. The choice of Q groups to be used depends on the type of reaction used to make the lacquer resin or molding composition resin used. Desirably, radical curing (r
acrylate, methacrylate, allyl or maleate (malcin).
ata) group is preferred. In epoxy resins, hydroxyl or carboxyl groups are recommended. Hydroxyl groups in polyurethane are preferred when the polysiloxane of the present invention is used in the hydroxyl group-containing resin portion.

However, isocyanate groups are preferred when the polysiloxane is used in the isocyanate-bearing resin portion of the present invention. In polyurethane systems that can be reacted very quickly with suitable catalysts, reactive injection molding processes (+?1M-process or RRIM-process)
In this case, carboxylate salts of carboxylate ester hexagonal polysiloxanes are used for a-effect.

If a cosb-like siloxane is used, ie if the D group represents a -Z-R-Q group, y is at most 4, preferably at most 3, in a-effect. In so-called linear siloxanes, the carboxylate ester groups are only at the two ends of the siloxane chain. In this case, X indicates 6 to 50,
Preferably it shows 8-32.

Linear siloxanes are utilized in the polysiloxanes of the invention produced by condensation action, since further polycondensation and incorporation of polysiloxane units is essentially avoided by carrying out the reaction in a controlled manner. This is the material. The homogeneity of such products is confirmed by GPC studies.

"Average molecular formula J (avoragea
+oleular rora+ula) is to be understood as meaning that the substance dowels molecules that essentially correspond to the structure of the formula. However, as known to those skilled in the art, small side reactions cannot be completely eliminated. The requirements of the present invention can be considered fulfilled with at least 75% production of the desired compound. and the remainder exists as homologous series or by-products of such compounds.

If comb-shaped products with y greater than 2 are reacted in such a condensation process, a crosslinking reaction takes place, as is known to those skilled in the art. To that extent, it is self-effective to essentially use only comb-shaped polysiloxanes with y of 1 to 2, and to carry out the condensation reaction in stages to essentially suppress the crosslinking reaction.

As a result, the initial siloxane is preferably used as a ring-opening ester with a lactone, for example in formula [11], 'JA (Il! -OH functional polysiloxane which can be converted into the polyester-containing α-polysiloxane of the present invention by chemical reaction.

Hereinafter, the present invention will be explained based on Examples, but the present invention is not limited only to these Examples.

Example 1 In a reaction vessel equipped with a stirrer and a reflux condenser, polysiloxane 589. (0.5 mol) was reacted with 571 g (5.0 mol) of epsilon-caprolactone after adding 100 ppffl of dibutyltin dilaurate under a nitrogen atmosphere heated to 160°C. After reacting for 6 hours, an organopolysiloxane having the average formula:

The hydroxyl value was 17 g (48n+gKOH), and the saponification value was 252LQgKOH/f.

Example 2 In the same manner as in Example 1, average formula: 143a+gKOH/g hydroxyl value 143a+gKOH/g 393sr (0.5 mol) of siloxane was reacted with 457g (4 mol) of epsilon-caprolactone. An organopolysiloxane having the average formula:

The hydroxyl value was 0 (fIIIg KOH/g, and the saponification value was 254IRg KO) I/g.

Example 3 In the same manner as in Example 1, 488 g (0.25 mol) of polysiloxane having the average formula: a and a hydroxyl value of 57 mg KOH/g was converted into epsilon-
React with 856 g (7.5 mol) of caprolactone,
The organopolysiloxane produced has a hydroxyl value of 20 mg KOII/g and a saponification value of 32,511 g KOJI/g. 837 g (0.5 mol) of polysiloxane containing 1 mg KOII/g was reacted with 1001.2 g (I0 mol) of delta-valerolactone, resulting in a solid content of 9G, 5%, and a hydroxyl value of 29 mg KO)I.
An organopolysiloxane having the average formula: with a saponification value of 300 mg KOH/g was produced.

Example 5 In the same manner as in Example 1, polysiloxane 90i (0.33 mol) having the average formula: and a hydroxyl value of 62 g KOH/g was reacted with 912 g (3 mol) of epsilon-caprolactone, Hydroxyl value is 31mgKOH/g, saponification value is 239w KOH
An organopolysiloxane having the average formula: /g was produced.

Example 6 In the same manner as in Example 1, polysiloxane 944sr (0.2 mol) having the average formula: and a hydroxyl value of 59 g KOH/g was converted into epsilon-
React with 1140 g (I0 mol) of caprolactone,
Hydroxyl value is 25mg KOH/g s Saponification value is 27
An organopolysiloxane with an average formula of 4 mg KOH/g was produced.

Example 7 In a reaction vessel equipped with a stirrer and a water separator, 717 g (0.5 mol) of a polysiloxane having the average formula: and a hydroxyl value of 78a+g KOH/g were added to adipic acid 6
7g (32 mol), 180g of 1,4-butadiol (
2 mol) and 300 g of xylene, then p-
) Added 3 g of diene sulfonic acid and heated to 140°C.
After reacting for an hour (main water content: 91 g: theoretical water yield: 90 sr), xylene and excess adipic acid were removed under vacuum. The organopolysiloxane produced has an average formula: % formula %, an acid value of 45 mg KOH/g and a saponification value of 2
02 mg KOJI/g.

Example 8 In the same manner as in Example 7, 499 g (0.25 mol) of polysiloxane having the average formula: Adipic acid 29
2 g (2.0 mol) to produce an organopolysiloxane having the average formula:

The hydroxyl value of the resulting organic product is 28+sg KOH/
The saponification value was 237 mg KOH/g.

Example 9 In the same manner as in Example 7, polysiloxane 495sr (0.5 mol) having the average formula: Reaction with 5-pentadiol 104r (I,04 mol) produced an organopolysiloxane having the average formula:

The resulting product had an acid value of 65 mg KOH/g and a saponification value of 185 OH/g.

Example 10 In the same manner as in Example 7, 791 g (0.5 mol) of polysiloxane having the average formula:
0 g (4,2 mol) and 1,6-hexadiol 3
54 g (3 moles) to produce an organoborisiloxane with an average formula: % formula %. The resulting product had an acid value of 38.5 mg KOH/g and a saponification value of 27 tmg KO)I/g.

Example 11 In the same manner as in Example 7, polysiloxane 615 with the average formula: and a hydroxyl value of 91 g KOH/g was prepared. (0.5 mol), phthalic anhydride 4
49g (3 moles) and neopentyl glycol 333
g (3.2 mol) to produce an organopolysiloxane having an average formula: % formula %.

The resulting product had a hydroxyl value of 39+agKO) and 17 g, and a saponification value of 251 ngKOH/f.

Example 12 In a reaction vessel equipped with a stirrer and water +'it 2 g, 710 g (0.5 mol) of a polysiloxane with the average formula: and an amine value of 78 mg KOII/g are mixed with adipic acid 14
8 g (I mol) and 100'C while bubbling nitrogen.
heated to. Approximately 18 sr (I mole) of water is separated and 95
After cooling to ℃, 208 g of 1,5-bentanediol (
2 mol) and 307 g (2.1 mol) of adipic acid were added. The reaction mixture was then again heated to 160'C. After reacting for 3 hours, approximately 72 g (4 mol) of water was separated. After creating a vacuum (20ml+), excess adipic acid is removed at suB temperature.
It was removed at 180°C. The organopolysiloxane produced had the average formula: and an acid value of 45a+g KOH/g and a tenation number of 179agKOH/g.

Example 13 In a reaction vessel equipped with a stirrer and a reflux condenser, 584 g of the organopolysiloxane synthesized in Example 1 (0,2
5 mol) with maleic anhydride 49K (0.5 mol) 1
The organopolysiloxane produced by reacting at 60°C within 4 hours has the average formula: and an acid value of 45 mg KOH/
g and saponification value of 207 mgKOH/g.

Example I4 In the same manner as in Example 13, organopolysiloxane+403y (0.25 mol) synthesized in Example 3 was reacted with phthalic anhydride'14 g (0.5 mol) to give an acid value of 1.
7+ng KOH/g and saponification value 3 l Omg
An organopolysiloxane was produced having the average formula: KOH/z.

Example 15 In a reaction vessel equipped with a stirrer and a reflux condenser, 803 g (0.5 mol) of the organopolysiloxane synthesized in Example 9 was mixed with 336 g of a 25%-Na)(CO:+ aqueous solution at room temperature). After addition of 250 g of toluene, the azeotrope with water was distilled off. After removal of the solvent by distillation, the resulting organopolysiloxane had the average formula: and an acid value of 0.7 mg KOH/ g and saponification value 18
0II1gKOf(/f.

Example 1G In the same manner as in Example 15, 24Gg (0.5 mol) of the organopolysiloxane synthesized in Example 13 was added.
5%-K) Reacted with 400g of lcO3 aqueous solution, acid value 0
．． 5a+g KOII/g and saponification 11Ili2
An organopolysiloxane with the average formula: contributing 04 mg KOII/g was produced.

Example 17 In a reaction vessel equipped with a stirrer and a reflux condenser, Example 13
1246g of organopolysiloxane (0
, 5 mol) was combined with 300 g of toluene and neutralized by adding with stirring 101 g of triethylamine (I, 0 mol). After removal of the solvent, the resulting organopolysiloxane, which grows the average formula:
lli 271mg KOH/g wok Lt:.

Example 18 Organopolysiloxane I (i!'i0g (0.25 mol) synthesized in Example 14 in the same manner as in Example 17)
87.5 g (0.5 mol) of benzyldimethylamine
An organopolysiloxane having a saponification value of 315 mg KOH/g was produced.

Example 19 In a reaction vessel equipped with a stirrer and a reflux condenser, 250 g of dry toluene and 8 toluene-2,4-diisocyanate
7 g (0.5 mol) and organopolysiloxane 5 synthesized in Example 3 (fig (0.1 mol)
was added dropwise within 60 minutes. After a post-reaction of 8 hours at ambient temperature, excess toluene-2,4-diisocyanate and toluene were removed under vacuum. The produced organopolysiloxane having the average formula: COOH
-Ingredients 1.5% and saponification value 320+ng KO) I/
I shot g myself.

Example 20 Organopolysiloxane 585K (0,2
5 mol) with 198 g (2.5 mol) of pyridine, 54.3 g (0.1 im mol) of acrylic acid chloride and 250 ppa+ of hydroquinone monomethyl ether, heated to 180°C and after 6 hours of post-reaction. ,
Excess acrylic acid chloride was hydrolyzed by adding water and extracted with water to remove it from the reaction mixture along with pyridine and pyridine hydrochloride.

After drying by azeotropic distillation, the organopolysiloxane produced has a saponification value of 242+++g
) [0) The iodine values of 17 g and 20 g iodine/toor were determined.

The following lacquer media were used in testing the polysiloxane additives of this invention. Percentages are by weight unless otherwise indicated.

Lacquer A (furniture lacquer) Fatty acid modified hydroxy polyester (Desmore Ko, t (Dasa+opban)
B)), ■ RD 181.75% melt j (Ji > 20
% hydroxypolyester, ■ (Desmofe, y (Desa+opbcn■) 1
200) 5% Cellulose acetobutyrate (Cell!t■) BP 300 10% solution) 4% Butyl acetate 16.4% Toluene 1296 Ethyl acetate 12% Ethyl glycol acetate 5. G% Hardening agent (Desmodur ■ (Dcsa+odur■) H
L 00 ) 25% total amount
100% curing condition: 1 at 80℃
0 minute lacquer B (acrylic/melamine lacquer) acrylic resin 50! 116 solution (Synlacryl■) Sc303
; Manufactured by Hoccbst) 43.4% melamine resin (SeLam1nc) US1
33; manufactured by 9yntbasc) 15.
5% pigment (Slcomin Red)
■) 1, 3030 S; 11 Made by ASPiL) 25
%, (D vent/ (n e n t o n e ■) paste 10% solution 2.5% xylene 4.6% aromatic hydrocarbons (boiling temperature range: 165-185°C) 6% aromatic hydrocarbons (Boiling temperature range: 186-215℃) 3% Total amount 100% Curing conditions: 130℃ for 20 minutes Lacquer C (coil coating lacquer) Oil-less polyester (Uralac ■) 107-RA B Niscad ( Scado) Made by Ff) 44.
5596T102 (RN 59; Bayer (Ba
20.35% melamine resin (Cyscl 301; manufactured by American Cyanasid) 4.7
0% p-) 40% solution of luenesulfonic acid in ethyl glycol acetate 0.25% Thinner (diluent) 30.15% Total amount 100% Curing conditions =
Lacquer D (UV curable lacquer) UV sensitive resin (Blex ■ (PIOX ■) 6 [117-0) for 60 seconds at 2BO℃
57.4% reactive thinner (Blex■ (Plcx■), G[11B-0)
38.3% Photoinitiator
r) (Irgacuro■ (lrgacuro■) 135
1) 2.996 Penzophenone
1.4% total amount 100
% curing conditions: 5 with 80W/cm high pressure mercury lamp
All! j/min UV curing lacquer E (graffiti resistant coating (Ant 1-Grar)
r i t iCoating)) Hydroxypolyester (Desmofene)
n ■) 6516796 solution)
31.2% ethyl glycol acetate
5.1% methoxybutyl acetate 3
．． 4% reaction accelerator (Desmorapld■ (Dcsmorapld■) PP 10% solution) [,2
% defoamer (Dcl'oaa+or)
0.2% TlO231.8% Bentonc 10% solution
2.1% hardening agent (DcsIIlodur■ IL 75% solution) 25
% total amount 100 % Curing conditions: Air dry at room temperature Lacquer F (release lacquer) Fatty acid modified hydroxy polyester (Desmopbcn■ 1300)
33.3% ethyl acetate
35.1% hardening agent (Dasmodur)
31, 6% total
100% curing conditions: 140°C for 60 seconds (sliding friction (lubricity) test) Apply one layer of lacquer approximately 40mm thick using a casting machine (lacquer A) and a spray applicator (lacquer B).
and Spiral Doctor (lacquers C and D), lacquer A was tested on furniture board test boards (size: H
em
) was applied.

After the lacquer film had hardened, the transparency of the lacquer film was determined by transmitting light. (This test was carried out separately with clear lacquers corresponding to pigmented lacquers).

After measuring the sliding friction, the lacquered surface was then cleaned with a mixture of naphtha and ethanol as a solvent, and the sliding friction was again measured in 4P1 using the method described below.
Established.

The polysiloxanes according to the invention listed in Table 1 were added to the lacquer.

As a comparative example, the following commercially available polysiloxanes were added to the lacquer.

Comparative Example 1 Low molecular weight polydimethylsiloxane (Ba
ysilon ■) M 50) Comparative example 2 Polyoxyalkylene polysiloxane copolymer (Buek ■ (I3yk ■) 300) Comparative example 3 Alpha, omega-hydroxyalkyl polydimethylsiloxane (Baysilon ■ (Baysilon ■) 0F10H502) The results are It is shown in Table 1.

The "
The following precision measurement method was used as an alternative to the "fingernail test" or measurement of the angle at which the cylinder slides off the coating.

Electromembrane drafting device (cla
ctric rilm drawing appara
tus) was used. The push burqa converter was attached to the delineating membrane installation. All sliding bodies can be drawn using the til + constant amplifier in the plotter.
A force transducer transferred the resistance encountered by the ies). The sliding body was moved in the direction of the push and pull over the surface to be measured. In addition, a hollow cylinder covered with a limited area of felt base on the sliding surface and filled with weights or iron balls was used as the sliding body.

(According to the fM concept of the above-mentioned ap + constant device, the 71111 constant is installed with matte black synthetic plastic plates such as those used in friction tests for emulsion paints, to avoid changing the weight of the sliding body. A limited area of surface 1- was varied at different speed levels.A glass plate was used as a support for the lacquer wave film when testing various additives.

(Measurement Results) Comparing the measured values, it was found that sliding resistance increases in proportion to the height of the sliding body. In addition, it was found that even when the speed of the Al11 suspension moved over the surface was increased by a factor of four, it did not affect the results. When the measurement results were plotted on a graph, a straight line passing through the zero point resulted.

Repeated measurements on different surfaces always yielded similar curves. The surface sliding properties (frictional properties) and curvature matched. This is because the aF+ method produces results with reliable reproducibility. In practice, this means that the characteristics expressed by objective numerical values can be measured accurately and quickly.

Slip resistance is expressed in ζ degrees in Newtons (V).

(Anti-Grarritti coating test method) A lacquer film approximately 80 JJm thick was applied by spraying onto an asbestos cement board pretreated with a primer measuring 50 cm x 50 cm square. Doweled into the lacquer were the additives shown in Table 2. After the lacquer film had completely cured (approximately 7 hours of molding), the following tests were carried out using various commercially available spray paints.

(b) Graffiti resistance - visual inspection of the action of the paint film (b) Visual test of the wet layer properties of the undercoat by spraying the applied spray paint onto the paint film. 2. If the paint is completely thin... 1. The spray paint is graffiti resistant. 2. If the spray paint has a tendency to form small droplets and accumulate... 2. The spray paint is graffiti resistant. If droplets accumulate on the paint film...3 V ~ Graffiti resistance Adhesion of spray paint to paint film After removing the used spray paint five times with ethyl glycol acetate, the above test (0) and (/~ were repeated.

The results are shown in Table 2.

(Internal Release A
Polyurethane-rim: reaction injection ψ molding (Pυ
ni-HM: roaction Injcctlon
molding) 320g with a thickness of 0, 1 am
308111 x 30cm with aluminum foil attached
X O, placed in a 3 cm aluminum mold and heated to 50°C. After 5 minutes of reaction, remove the test plate and
The attached aluminum piece was peeled off at a speed of 30 cm per minute.

The force required for this peeling operation (peel adhesion force (peel adhesion force)
el atll+esion)) was determined as 1p1. Additionally, the reaction initiation time (time after isocyanate addition until foaming starts) and compatibility (solubility) of the polysiloxane utilized in the polyol compound were tested.

As a comparative example, the following materials were used.

Comparative Material (Materia+) 1 2 U.S. Patent No. 4.
Example of Specification No. 070.695 (ExaIlple)
1 Comparative substance (Jubstancc) 2: Example of European Patent No. 103.367 (lExafflp
lc) 2 Comparative Substance 3: Example of European Patent No. 110.900 (Test 1) (lExaBlc) 1 Table 3 shows the nature and amount of each of the substances used and the results obtained. .

(Polyurethane-rim formulation (PUR-
Wyandotta Pluracol (g)
) 380) 44.34% 1.4-butadiol 8.8G! '6 Wednesday
0.0
7% DABCO■ (DABCO"')
0.22% dibutyltin dilaurate 0.01% isocyanate (Upjobn l5onatc■) 181)
4G, 5,”6 total amount
100% (Test method for release lacquer) Approximately 8y/nfm release lacquer was applied with a 15μm doctor.
It was coated on Pergamin paper and cured in a paint dryer at 140°C for 60 seconds to a non-tacky thickness of 4 m. The following tests were conducted at that time.

(a) Peeling value at 20°C and 70°C (I? cloa
sc Value) (b) Measurement of residual viscosity (I) release value (Release Value) 3
cm-wide self-sticking (scl"-stl
cklng) adhesive tape was used on paper coated with a release lacquer for 24 hours at 20°C or 70°C.
A load was applied with a CD weight. After cooling to 20° C., the adhesive tape was peeled off at an angle of 180@ and at a rate of 60 Cnl/min.

The force required for this peeling was determined as ΔP1.

(2) Measurement of Residual Adhesive Strength The peeled-off adhesive piece with the peel value was attached to a clean glass plate, and 20 g/ca of 6:J city was applied for 24 hours. The adhesive strip was then peeled off as described in the Peel Value Test. A piece of adhesive that did not apply pressure to the overturned paper was pasted on the glass as a base $ value, and the test value for this piece was 1.
0096 value was assigned. The results are shown in Table 4.

[Margin below]

Claims (1)

[Claims] 1. Average formula (I) for the amount that produces effective non-adhesive properties and increases lubricity: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A group, B group and The D groups each represent a -CH_3 group or a -Z-R-Q group, and the Z group is an alkylene group having 1 to 11 carbon atoms, -(CH_2)_2SCH
Represents a _2- group or a -(CH_2)_3NHCO- group; the R group contains at least 3 carboxylate ester bonds and has an average molecular weight of 300 to 3000 @Mn@
represents an aliphatic group, a cycloaliphatic group, or an aromatic group having the following: Q group represents a reactive group capable of chemically reacting with the resin component of the resulting composition; x is 4 to 150, y is 1 ~6; the average molecule contains at least one -Z-R-Q group, and the ratio of the number of -Z-R-Q groups to the number x is from 1:3 to 1:3
A lacquer or molding composition comprising a polyester-containing polysiloxane (0). 2. The composition according to claim 1, wherein the carboxylate ester bond in the R group is bonded by a difunctional hydrocarbon group having 2 to 12 carbon atoms. 3. The composition according to claim 2, wherein the carboxylate ester bond in the R group is bonded by a difunctional hydrocarbon group having 4 to 6 carbon atoms. 4. The composition of claim 3, wherein the carboxylate ester bond in the R group is bonded by a saturated aliphatic hydrocarbon group containing 5 carbon atoms. 5. The composition according to claim 1, wherein the R group represents a polycaprolactone group. 6. The composition according to claim 1, wherein the A and B groups represent a -Z-R-Q group, and the D group represents a -CH_3 group. 7 The ratio of the number of -Z-R-Q groups to the number x is 1:3 to 1:
25. The composition according to claim 6, wherein the composition is 8 The ratio of the number of -Z-R-Q groups to the number x is 1:5 to 1:
15. The composition according to claim 7, wherein the composition is 15. 9 The above A and B groups represent -CH_3 group, and the D group represents -
A composition according to claim 1 exhibiting a Z-R-Q group. 10 The ratio of the number of -Z-R-Q groups to the number x is 1:3 to 1
:25. 11 The ratio of the number of -Z-R-Q groups to the number x is 1:4 to 1
:16. 12. The composition according to claim 1, wherein the Q group represents a group selected from the group consisting of -OH group, -COOH group, -NCO group, -CH=CH_2 group, and -C=CH_2 group. . 13 Average formula (I) for the amount that provides effective non-stick properties and improves lubricity: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I
) (In the formula, A group, B group and D group are each -CH_3
group or -Z-R-Q group, and the Z group has 1 to 11 carbon atoms.
represents an alkylene group, -(CH_2)_2SCH_2- group or -(CH_2)_3NHCO- group; R group is
Denotes an aliphatic, cycloaliphatic or aromatic group containing at least 3 carboxylate ester bonds and having an average molecular weight of 300 to 3000; represents a reactive group capable of reacting with; x represents 4 to 150, y represents 1 to 6; the average molecule is
contains at least one -Z-R-Q group, -Z-R-
the ratio of the number of Q groups to the number x is from 1:3 to 1:30). A method for imparting non-stick properties to loose compositions and improving their lubricity.